Experimental Study of C2Cl3+NO2 Reaction

The free radical reaction of C2Cl3 with NO2 was investigated by step-scan time-resolved FTIR (TR-FTIR) emission spectroscopy. Due to the vibrationally excited products of Cl2CO, NO, and CO, strong IR emission bands were observed with high resolution TR-FTIR spectra. Four reaction channels forming C2Cl3O+NO, CCl3CO+NO, CO+NO+CCl3, and ClCNO+Cl2CO were elucidated, respectively. Spectralˉtting showed that the product CO was highly vibrationally excited with the nascent average vibrational energy of 60.2 kJ/mol. Possible reaction mechanism via intermediates C2Cl3NO2 and C2Cl3ONO was proposed.     

Reactions of Cl2P3/2: Absolute rate constants for reaction with H2, CH4, C2H6, CH2Cl2, C2Cl4, and c?C6H12

The absolute rate constants have been measured for several gas-phase chlorine atom-molecule reactions at 25°C by resonance fluorescence. These reactions and their corresponding rate constants in units of cm³ mole^?1 sec^?1 are: The effects of varying the substrate pressure, total pressure, light intensity and chlorine-atom source on the value of the bimolecular rate constants have been investigated for all these reactions. Conditions under which no competing side reaction occurs were established and the reported rate constants were measured under these conditions. For reactions (2), (5), (6), (7), and 8, there is a discrepancy of a factor of two between the rate constants measured in this work and values in the literature; it is suggested that this is due to an error in the previously measured value of k/k upon which the relative measurements in the literature ultimately depend.     

First Polynuclear Palladium Compounds [(C5H12NO)(PdCl3)]n and [(C10H16NO)2(Pd2Cl6)] with High Antitumor and Radioprotective Activity

Russian Journal of Coordination Chemistry - Polymeric palladium complexes [(C5H12NO)(PdCl3)]n (I) and [(C10H16NO)2(Pd2Cl6)] (II) were synthesized for the first time and studied by X-ray...     

Computational study on the kinetics and mechanism for the unimolecular decomposition of C6H5NO2 and the related C6H5 + NO2 and C6H5O + NO reactions

The kinetics and mechanisms for the unimolecular dissociation of nitrobenzene and related association reactions C(6)H(5) + NO(2) and C(6)H(5)O + NO have been studied computationally at the G2M(RCC, MP2) level of theory in conjunction with rate constant prediction with multichannel RRKM calculations. Formation of C(6)H(5) + NO(2) was found to be dominant above 850 K with its branching ratio > 0.78, whereas the formation of C(6)H(5)O + NO via the C(6)H(5)ONO intermediate was found to be competitive at lower temperatures, with its branching ratio increasing from 0.22 at 850 K to 0.97 at 500 K. The third energetically accessible channel producing C(6)H(4) + HONO was found to be uncompetitive throughout the temperature range investigated, 500-2000 K. The predicted rate constants for C(6)H(5)NO(2) --> C(6)H(5) + NO(2) and C(6)H(5)O + NO --> C(6)H(5)ONO under varying experimental conditions were found to be in good agreement with all existing experimental data. For C(6)H(5) + NO(2), the combination processes producing C(6)H(5)ONO and C(6)H(5)NO(2) are dominant at low temperature and high pressure, while the disproportionation process giving C(6)H(5)O + NO via C(6)H(5)ONO becomes competitive at low pressure and dominant at temperatures above 1000 K.     

Rydberg electron transfer to C6H5NO2: lifetimes and characteristics of the product C6H5NO2- ions

The nature of electron binding in C6H5NO2- ions produced by Rydberg electron transfer in K(np)C6H5NO2 collisions is investigated through measurements of the number and the lifetimes of the product ions and their dependence on Rydberg atom velocity and principal quantum number n in the range 12 相似文献   

35Cl NQR and structural-dynamic properties of crystalline CCl3C(O)OC6H2Cl3-2,4,6

The temperature dependences of the resonance frequency and quadrupole spin-lattice relaxation time of the chlorine-35 nuclei in crystalline CCl₃C(O)OC₆H₂Cl₃-2,4,6 were studied. Owing to the presence of resonant nuclei in various fragments of the molecules, the character of dynamics of these molecular fragments and the entire molecule was established. It is shown that thermal librations of molecules are quasiharmonic over the whole temperature range from 77 K to the melting point of the crystal. The reorientational motion of the CCl₃ group bonded to the three-coordinated carbon atom was revealed. This motion causes an exponential increase in the spin-lattice relaxation time of the chlorine nuclei of this group and subsequent damping of NQR signals (chlorine-35 resonance signals of the aryl radical were observed before melting of the sample). The activation energy of the reorientational motion is found; its value, which is 27.3 kJ/mole, is considered in comparison with the activation energies obtained by the Cl NQR method in solids for CCl₃ reorientations in similar molecular structures.     

Reactions between rubidium atoms and C6F6, C2Cl4, C2HCl3, CH2=CCl2 or trans-C2H2Cl2 in crossed molecular beams

Molecular and fragment negative ions are produced from the collisions between rubidium atoms and several kinds of halogenated unsaturated organic molecules in crossed supersonic beams. Their apparent electron affinities and the bond dissociation energies are measured.